CN102391531B - Electrostatic self-assembled multilayer film and preparation method thereof - Google Patents
Electrostatic self-assembled multilayer film and preparation method thereof Download PDFInfo
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- CN102391531B CN102391531B CN 201110185719 CN201110185719A CN102391531B CN 102391531 B CN102391531 B CN 102391531B CN 201110185719 CN201110185719 CN 201110185719 CN 201110185719 A CN201110185719 A CN 201110185719A CN 102391531 B CN102391531 B CN 102391531B
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Abstract
The invention provides a high-nano-content compound formed by diazo-containing polyelectrolyte and montmorillonite nanoparticles through electrostatic interaction and a preparation method thereof. The preparation method comprises steps as follows: diazo-containing polyelectrolyte and lamellar-structure inorganic nanoparticles are subjected to electrostatic compounding in a water phase to obtain a multilayer film, and the multilayer film is crosslinked by light radiation and/or heating. The composite film has the advantages of light weight and high strength; and the self-assembling method is simple to operate and has the advantage of controllable structure.
Description
Technical field
The present invention relates to that a kind of in the inorganic-organic composite material contains the diazo polyelectrolyte and the montmorillonite-based nano ion forms mixture of high nanoparticle content and preparation method thereof by electrostatic interaction.
Background technology
The electrostatic adhesion self-assembling technique is the technology of a kind of novelty and maturation, easy preparation nano film material, is widely used for preparing various film material with function.The polymkeric substance of two kinds of oppositely chargeds, nanoparticle can attract each other by electrostatic adsorption, by alternately soak the self-assembled multilayer film that just can successively be grown in the polymers soln of these two kinds of oppositely chargeds.This method for preparing film is simple to operate, and film forming efficiency is high, and the film internal structure has certain regularity, and thickness is controlled and can be in various flexible surfaces assemblings, so be a kind of technology platform of high efficiency, low cost.
Polynite has good dispersing property, can widespread use macromolecular material industry as the additive of nanometer polymer macromolecular material, improve shock resistance, antifatigue, dimensional stability etc., thereby play the effect that strengthens polymkeric substance comprehensive physical performance, improve simultaneously the materiel machining performance.Simultaneously, polynite is the clay that a kind of interlayer contains exchangeable cation, and in the presence of a large amount of water, the polynite crystal layer is surrounded by water molecules, and the crystal layer stable suspersion is scattered in the water, forms colloidal solution.When adding cationic polymkeric substance, can produce electrostatic adsorption with electronegative polynite crystal layer.Patent 200610124485.0 and 200910010950.1 discloses the method that a kind of chitosan quaternary ammonium salt and polynite prepare nano material.Patent 200810222210.X discloses the method that ammonium polyphosphate and polynite prepare nano composite material, and the material that obtains has good flame retardant resistance.Patent 200910023236.6 discloses the preparation method of diallyl containing quaternary ammonium salt modified montmorillonoid, both because its cationic can be carried out intercalation, again because it contains the non-conjugated dienes key, cyclopolymerization can occur between cheating engaging layer, generates the polymkeric substance that contains five-membered cyclic.
Diazonium salt is widely used in organic, Polymer Synthesizing.Diazonium salt can decompose under the condition of heat or light, decomposes to produce free radical, and intermolecular reaction can occur, and obtains the material of internal crosslinking, is conducive to improve the mechanical property of material.In recent years, the polymkeric substance that contains the diazonium salt group is used to prepare crosslinked self-assembled multilayer film.
Utilize the electrostatic interaction between polynite and the polymer diazonium salt to obtain composite membrane of polymer, under the irradiation of UV-light, crosslinking reaction occurs, make the reactive force between film and the film become covalent bonds, improve stability and the mechanical property of film.
Summary of the invention
Technical problem to be solved by this invention is to be to provide a kind of polynite and diazonium salt excellent properties separately that utilizes to prepare light-weight high-strength material, provides a kind of simple to operate, the self-assembling method that structure is controlled.
In order to solve the problems of the technologies described above, the invention provides electrostatic self-assembled multilayer film of a kind of crosslinkable polyelectrolyte and layered inorganic nanoparticle and preparation method thereof.
The electrostatic self-assembled multilayer film of crosslinkable polyelectrolyte and layered inorganic nanoparticle comprises: the crosslinking structure of polyelectrolyte and inorganic nano-particle, it is by with the polyelectrolyte that contains diazonium groups and the inorganic nano-particle of laminated structure, obtain multilayer film at aqueous phase by the compound mode of static, the mode by rayed and/or heating makes film crosslinked.
The preparation method of the electrostatic self-assembled multilayer film of crosslinkable polyelectrolyte and layered inorganic nanoparticle is by with the polyelectrolyte that contains diazonium groups and the inorganic nano-particle of laminated structure, obtain multilayer film at aqueous phase by the compound mode of static, the mode by rayed and/or heating makes film crosslinked.
The invention discloses electrostatic self-assembled multilayer film of a kind of crosslinkable polyelectrolyte and layered inorganic nanoparticle and preparation method thereof, prepared excellent material performance, preparation manipulation is simple, and structure is controlled.
Description of drawings
Fig. 1 is the SEM after resulting polymers ionogen and the montmorillonite composite UV-irradiation in the embodiment of the invention 1.
Fig. 2 is the SEM after resulting polymers ionogen and the montmorillonite composite UV-irradiation in the embodiment of the invention 2.
Embodiment
Describe embodiments of the present invention in detail below with reference to drawings and Examples, how the utilisation technology means solve technical problem to the present invention whereby, and the implementation procedure of reaching technique effect can fully understand and implements according to this.
The preparation method of the electrostatic self-assembled multilayer film of crosslinkable polyelectrolyte and layered inorganic nanoparticle, it is characterized in that containing the polyelectrolyte of diazonium groups and the inorganic nano-particle of laminated structure, obtain multilayer film at aqueous phase by the compound mode of static, the mode by rayed and/or heating makes film crosslinked.
Described to contain diazo homopolymer polyelectrolyte be the polystyrene that diazo replaces, and poly-methyl-vinylbenzene passes through high molecular weight reactive: nitrated, reduction, diazotization obtain.
It is described that to contain diazo multipolymer polyelectrolyte be to contain diazo to obtain the segmented copolymer of phenyl, random copolymers.As with ABS, SBS, pass through high molecular weight reactive: nitrated, reduction, diazotization obtain.
It is described that to contain diazo blend polyelectrolyte be that one or more are used simultaneously with above-mentioned polyelectrolyte, also can with other non-diazo polyelectrolyte, such as chitosan, polymine is used simultaneously.
Described laminar nano ion can be the inorganic nano-particle of any electronegative laminated structure, preferred electronegative polynite.
Described containing in the mixed solvent that diazo polyelectrolyte is dissolved in deionized water, deionized water and organic solvent (such as acetone, tetrahydrofuran (THF), DMF etc.).
Described laminar nano ion makes it to be dispersed in the deionized water with the form of individual layer by repeated ultrasonic, vigorous stirring, and the time is no less than 1 day, and mass concentration is 0.0001～1.0%.
Described multilayer complex films prepares by the mode of nanoparticle dispersion liquid-deionized water-polyelectrolyte solution-deionized water circulation immersion, each soak time 1～10 minute, and the number of plies is 10～300 layers, 1 micron～1 millimeter of thickness.
Described substrate is glass, silicon chip, quartz, glass fibre.
Described substrate makes surface charging by chemical reaction, for example: at first utilize sulfuric acid, hydrogen peroxide to make the surface with hydroxyl, utilize afterwards amino estersil to make the surface with positive electricity.
Described disposal multi-layer composite membrane forms nano-particle compound by mix nanoparticles dispersion liquid and polyelectrolyte solution.
Described nano-complex is by natural subsidence, and centrifugal, membrane filtration obtains.
Described mixture makes it crosslinked by UV-irradiation, obtains stable material, wavelength region 200～380nm.
Described mixture makes it crosslinked by heating, obtains stable material, 70～200 ℃ of Heating temperatures.
The material of gained of the present invention contains inorganic nano-particle content 40～90%, has the performance of high-strength light, and its fire resistance is good simultaneously, can be used under the abominable condition of circumstance complication.
Following examples are detailed description of the invention, can not be interpreted as it is restriction to technical solution of the present invention.
Example 1
The processing of silicon chip:
A. used the alcohol ultrasonic cleaning 10 minutes.
B. use H
2SO
4(98%): H
2O
2(30%)=3: 1 (volume ratio) under the condition of boiling, processed 20 minutes.
C. soaked 5 minutes with deionized water.
D. use the aqueous solution soaking 2 hours of the aminopropyl trimethoxysilane of massfraction 20%.
E. soaked 5 minutes with deionized water
F. use N
2Dry up.
The preparation of polynite colloidal solution
The 0.5g polynite is scattered in the 100mL water, uses supersound process 15min, high-speed stirring 8h so circulates 8 times afterwards, carries out at last centrifugally, and it is stand-by to get upper strata liquid.
The preparation of polystyrene diazonium salt solution
The 1.0g polystyrene is dissolved in the 25mL chloroform, adds the dense HNO of 8mL
3With the dense H of 3mL
2SO
4Mixing acid, reaction 12h obtains poly-p-nitrophenyl ethene, with 10mL DMF dissolving, N
2Protection is lower, joins 13.0g SnCl
2With the mixing solutions of the dense HCl of 20mL, 100 ℃ of reaction 24h.Reaction precipitates in 200mL ethanol after finishing, and obtains poly-p-aminophenyl ethene.The poly-p-aminophenyl ethene that obtains is dissolved in the 20mL water, adds the 2.8mL concentrated hydrochloric acid, temperature remains on 0-5 ℃, adds 10mL NaNO
2(1.2g) aqueous solution, reaction 6h obtains the polystyrene diazonium salt solution, hides in refrigerator and cooled and preserves.
The electrostatic self-assembled of polyelectrolyte and polynite
30mL polynite solution (0.1%) and 30mL polystyrene diazonium salt solution (1.5%) are placed respectively two 50mL beakers.First the silicon chip of handling well is soaked 10min in polynite solution, put into deionized water after the taking-up and soak 10min, in the polystyrene diazonium salt solution, soak 10min afterwards, put into deionized water after the taking-up and soak 10min.This process that circulates 30 times.The composite membrane that obtains is shone 5min under ultraviolet lamp.
Example 2
The preparation of polyelectrolyte solution and polynite colloidal solution is the same.
10mL polynite solution (0.1%) is joined 10mL polystyrene diazonium salt solution (1.5%) in solution, ultrasonic mixing 0.5h, filter membrane with 0.45 μ m filters, and obtains polymkeric substance, inorganic nano-particle composite membrane, and the composite membrane that obtains is shone 5min under ultraviolet lamp.
Claims (6)
1. the preparation method of the electrostatic self-assembled multilayer film of the inorganic nano-particle of a crosslinkable polyelectrolyte and laminated structure, it is characterized in that containing the crosslinkable polyelectrolyte of diazonium groups and the inorganic nano-particle of laminated structure, obtain multilayer film at aqueous phase by the compound mode of static, mode by rayed and/or heating makes film crosslinked, the inorganic nano-particle of laminated structure is electronegative polynite, containing diazo crosslinkable polyelectrolyte is dissolved in the deionized water, electronegative polynite is dispersed in the deionized water with the form of individual layer, film is carried out rayed adopt UV-light when crosslinked, wavelength region 200-380nm, when film was carried out heat cross-linking, Heating temperature was 70-200 ℃.
2. preparation method as claimed in claim 1 is characterized in that, described to contain diazo crosslinkable polyelectrolyte be homopolymer, multipolymer or blend.
3. preparation method as claimed in claim 1 is characterized in that, described multilayer film by alternating deposit in substrate; Or by disposable compound the obtaining of solution.
4. preparation method as claimed in claim 3 is characterized in that, the inorganic nano-particle that will contain the polyelectrolyte of diazonium groups and laminated structure in solution disposable compound after, centrifugal by natural subsidence, membrane filtration obtains multilayer film.
5. preparation method as claimed in claim 1 is characterized in that by A or the preparation of B method:
A:1) preparation crosslinkable polyelectrolyte solution and polynite colloidal solution;
2) make substrate charged by chemical reaction;
3) substrate is alternately immersed in crosslinkable polyelectrolyte solution and the polynite colloidal solution, after polyelectrolyte solution and polynite colloidal solution are immersed in substrate, substrate is immersed in the deionized water;
4) multilayer film is exposed crosslinked;
B:1) preparation polyelectrolyte solution and polynite colloidal solution;
2) mix crosslinkable polyelectrolyte solution and polynite colloidal solution and obtain composite membrane;
3) expose crosslinked to the composite membrane that obtains.
6. the electrostatic self-assembled multilayer film of the inorganic nano-particle of a crosslinkable polyelectrolyte and laminated structure, it comprises: the crosslinking structure of the inorganic nano-particle of crosslinkable polyelectrolyte and laminated structure is characterized in that, by the method preparation of claim 1.
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| CN106729997A (en) * | 2017-01-12 | 2017-05-31 | 温州医科大学 | A kind of preparation method of the polymer multilayer film of organic inorganic hybridization controlled release antibacterials |
| CN109777381A (en) * | 2017-11-13 | 2019-05-21 | 中石化石油工程技术服务有限公司 | A kind of method that montmorillonite self assembly is deposited on the surface of solids |
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